US6488867B1 - Organic fluorescent whitening pigment composition having an excellent hiding power - Google Patents
Organic fluorescent whitening pigment composition having an excellent hiding power Download PDFInfo
- Publication number
- US6488867B1 US6488867B1 US09/394,502 US39450299A US6488867B1 US 6488867 B1 US6488867 B1 US 6488867B1 US 39450299 A US39450299 A US 39450299A US 6488867 B1 US6488867 B1 US 6488867B1
- Authority
- US
- United States
- Prior art keywords
- pigment
- fluorescent whitening
- group
- present
- organic pigment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 83
- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 230000002087 whitening effect Effects 0.000 title claims abstract description 29
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims description 19
- 239000012860 organic pigment Substances 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000004816 latex Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000001293 FEMA 3089 Substances 0.000 claims description 2
- 150000002366 halogen compounds Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 2
- -1 methoxy, ethoxy, sulfo group Chemical group 0.000 abstract description 11
- 239000001023 inorganic pigment Substances 0.000 abstract description 9
- 239000000306 component Substances 0.000 description 48
- 239000012463 white pigment Substances 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 21
- 238000000576 coating method Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 0 *C.*C.Cc1ccc(C=Cc2ccccc2S(=O)(=O)[O-])cc1.Cc1ccc(C=Cc2ccccc2SOO[O-])cc1.[1*][N+]([2*])([3*])[4*] Chemical compound *C.*C.Cc1ccc(C=Cc2ccccc2S(=O)(=O)[O-])cc1.Cc1ccc(C=Cc2ccccc2SOO[O-])cc1.[1*][N+]([2*])([3*])[4*] 0.000 description 14
- 239000000976 ink Substances 0.000 description 14
- 239000006081 fluorescent whitening agent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- FEWWJVHYSXNMTD-UHFFFAOYSA-L CCCCCCCCCCCC[N+](C)(C)Cc1ccccc1.O=S(=O)([O-])c1ccccc1C=Cc1ccc(-c2ccc(C=Cc3ccccc3SOO[O-])cc2)cc1 Chemical compound CCCCCCCCCCCC[N+](C)(C)Cc1ccccc1.O=S(=O)([O-])c1ccccc1C=Cc1ccc(-c2ccc(C=Cc3ccccc3SOO[O-])cc2)cc1 FEWWJVHYSXNMTD-UHFFFAOYSA-L 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
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- 239000011347 resin Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XDRLAGOBLZATBG-UHFFFAOYSA-N 1-phenylpenta-1,4-dien-3-one Chemical compound C=CC(=O)C=CC1=CC=CC=C1 XDRLAGOBLZATBG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N CCc1ccccc1 Chemical compound CCc1ccccc1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- ZMLPKJYZRQZLDA-UHFFFAOYSA-N 1-(2-phenylethenyl)-4-[4-(2-phenylethenyl)phenyl]benzene Chemical group C=1C=CC=CC=1C=CC(C=C1)=CC=C1C(C=C1)=CC=C1C=CC1=CC=CC=C1 ZMLPKJYZRQZLDA-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- SHKZXLWRWJESJT-UHFFFAOYSA-N C.C.C.CCCCCCCCCCCCCCCCCC[N+]1=CC=C(C)C=C1.CCCCCCCCCCCC[N+](C)(C)C Chemical compound C.C.C.CCCCCCCCCCCCCCCCCC[N+]1=CC=C(C)C=C1.CCCCCCCCCCCC[N+](C)(C)C SHKZXLWRWJESJT-UHFFFAOYSA-N 0.000 description 1
- JRZOFPQKYHHGIC-UHFFFAOYSA-O C1CC[NH2+]C1.[HH] Chemical compound C1CC[NH2+]C1.[HH] JRZOFPQKYHHGIC-UHFFFAOYSA-O 0.000 description 1
- YJEFPXYDGUDLJH-UHFFFAOYSA-O C1COCC[NH2+]1.[HH] Chemical compound C1COCC[NH2+]1.[HH] YJEFPXYDGUDLJH-UHFFFAOYSA-O 0.000 description 1
- FKNQCJSGGFJEIZ-UHFFFAOYSA-O CC1=CC=[NH+]C=C1 Chemical compound CC1=CC=[NH+]C=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-O 0.000 description 1
- HROHFGIWHFZABX-UHFFFAOYSA-G CCCCCCCCCCCCCCCCCCN(C)(C)CCCCCCCCCCCC.CCCCCCCCCCCCN(C)(C)C.CCCCCCCCCCCCN(C)(C)Cc1ccccc1.CCCCCCCCCCCCN1(C)CCOCC1.CCN(CC)(CC)CC.CN(C)(C)c1ccccc1.C[N+](C)(C)C.[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[HH] Chemical compound CCCCCCCCCCCCCCCCCCN(C)(C)CCCCCCCCCCCC.CCCCCCCCCCCCN(C)(C)C.CCCCCCCCCCCCN(C)(C)Cc1ccccc1.CCCCCCCCCCCCN1(C)CCOCC1.CCN(CC)(CC)CC.CN(C)(C)c1ccccc1.C[N+](C)(C)C.[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[HH] HROHFGIWHFZABX-UHFFFAOYSA-G 0.000 description 1
- FCMBTMPVRHEYGK-UHFFFAOYSA-L CCCCCCCCCCCCCCCCCCN1=CC=C(C)C=C1.CN1(C)CCCC1.[Cl-].[Cl-].[HH] Chemical compound CCCCCCCCCCCCCCCCCCN1=CC=C(C)C=C1.CN1(C)CCCC1.[Cl-].[Cl-].[HH] FCMBTMPVRHEYGK-UHFFFAOYSA-L 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- WQCCZCWFJKSBGM-UHFFFAOYSA-L O=S(=O)([O-])c1ccccc1C=Cc1ccc(-c2ccc(C=Cc3ccccc3SOO[O-])cc2)cc1 Chemical compound O=S(=O)([O-])c1ccccc1C=Cc1ccc(-c2ccc(C=Cc3ccccc3SOO[O-])cc2)cc1 WQCCZCWFJKSBGM-UHFFFAOYSA-L 0.000 description 1
- SQAKQVFOMMLRPR-AXPXABNXSA-N OS(c1c(/C=C\c(cc2)ccc2-c2ccc(/C=C\c3ccccc3S(O)(=O)=O)cc2)cccc1)(=O)=O Chemical compound OS(c1c(/C=C\c(cc2)ccc2-c2ccc(/C=C\c3ccccc3S(O)(=O)=O)cc2)cccc1)(=O)=O SQAKQVFOMMLRPR-AXPXABNXSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229920002689 polyvinyl acetate Polymers 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
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- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/41—Organic pigments; Organic dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0065—Organic pigments, e.g. dyes, brighteners
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
- D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/0004—General aspects of dyeing
- D06P1/0012—Effecting dyeing to obtain luminescent or phosphorescent dyeings
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/42—Coatings with pigments characterised by the pigments at least partly organic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
Definitions
- This invention relates to an organic fluorescent whitening pigment excellentin hiding power and more particularly, it is concerned with an organic fluorescent whitening pigment which can be utilized as coating agents for papers, coloring matters for aqueous or oily inks and inkjets, pigment components, for paints, etc., and which is capable of exhibiting excellent properties when applied to a use, in particular, needing high hiding power as well as high whiteness, for example, a coating agent for surface coating of a paper such as photographic printing paper.
- a pigment component of a white pigment there are mainly used inorganic materials, for example, titanium oxide, calcium carbonate, zinc oxide, clay, kaolin, talc, etc.
- inorganic materials for example, titanium oxide, calcium carbonate, zinc oxide, clay, kaolin, talc, etc.
- organic whitening pigment components having hiding power comparable to or more excellent than that of these pigments components.
- alkylenebismelamine derivatives have been proposed as disclosed in JP-A-6-122674, which, however, are excellent in hiding power but insufficient in whiteness because of having no fluorescence.
- White pigments consisting of inorganic materials of the prior art are excellent in hiding power, but when using these pigments for coating papers, for example, the whiteness of coated papers is not sufficient.
- various fluorescent whitening agents such as of bistriazinylaminostylbene type are ordinarily used, but this has some limitations, because the fluorescent whitening agents often meet with such a particular phenomenon as concentration quenching, i.e. that even if using in a concentration of more than certain value, not only more whitening effect cannot be obtained, but also a yellowish hue is rather given. Accordingly, the fluorescent whitening agent can only be used with a very low concentration.
- inorganic pigment components naturally have large densities and when preparing dispersed compositions therefrom, the pigment components tend to be separated and settled, so that a uniform and stable dispersed composition is hard to be prepared. This is not preferred from the stand-point of the storage stability of the pigment dispersed composition. Further, when such a pigment composition is coated onto a paper, for example, the weight of the coated paper is increased. In addition, the inorganic pigment generally has a disadvantage that its compatibility with binders and other reagents required for preparation of the pigment composition is inferior.
- organic fluorescent whitening pigment composition having an excellent hiding power, comprising, as a pigment component a complex salt (compound) represented by the following general formula:
- R 1 represents an alkyl, alkenyl, aralkyl, aryl or cycloalkyl group
- R 2 , R 3 and R 4 independently represent hydrogen atom or R 1 , two or three groups of R 2 , R 3 and R 4 being capable of forming a heterocyclic group with nitrogen atom in each case.
- the inventors have made various efforts to solve the above described disadvantages of the inorganic white pigments and consequently, have found that a complex salt obtained from some fluorescent whitening agent and quaternary ammonium compound has very excellent properties as an organic white pigment component.
- the present invention is based on this finding.
- An organic fluorescent whitening pigment composition having an excellent hiding power comprising, as a pigment component, a complex salt (compound) represented by the following General Formula:
- R 1 represents an alkyl, alkenyl, aralkyl, aryl or cycloalkyl group
- R 2 , R 3 and R 4 independently represent hydrogen atom or R 1 , two or three groups of R 2 , R 3 and R 4 being capable of forming a heterocyclic group with nitrogen atom in each case.
- the above described complex salt of the present invention is a substantially water-insoluble fluorescent complex salt, represented by the following general formula:
- Y represents a colorless, non-fluorescent, water-soluble anion or OH ⁇
- R 1 represents an alkyl, alkenyl, aralkyl, aryl or cycloalkyl group
- R 2 , R 3 and R 4 independently represent hydrogen atom or R 1 or R 2 , R 3 and R 4 can form a heterocyclic group with nitrogen atom in each case.
- an organic fluorescent whitening pigment excellent in hiding power can be obtained, consisting of this complex salt as a predominant component.
- compositions for fluorescent papers comprising the above described fluorescent complex salt mixed in coating compositions for papers, or fluorescent white ink compositions for ink jets comprising the above described fluorescent complex salt mixed in white ink compositions for ink jets, processes for the production of the same, methods of using the same, various materials using the same, in particular, coated papers having excellent hiding power and high whiteness, for example, photographic printing papers (photographic papers), etc.
- white pigment compositions for coating papers or plates clays, calcium carbonate, titnaium oxide, etc. have hitherto been used as a white pigment component. This is mainly due to the excellent hiding power that these white pigments have.
- the organic white pigment of the present invention has more excellent hiding power than the inorganic white pigments consisting predominantly of the above described materials. Further, the white pigment of the present invention is so fluorescent that when using the pigment, a higher whiteness that the prior art cannot reach can be obtained. In addition, this fluorescent property does not exhibit concentration quenching that appears in ordinary fluorescent whitening agents (such a peculiar phenomenon to fluorescent whitening agents that when using a fluorescent whitening agent with a concentration higher than a certain value, the whitening effect is rather lowered to render yellowish sometimes). Thus, the white pigment of the present invention can be used in such a high concentration that cannot be considered in the prior art.
- the fluorescent whitening pigment component of the present invention has a smaller density, because of being organic, than inorganic pigments. Accordingly, in the case of forming an aqueous dispersion, for example, the pigment component is hard to be settled and the storage stability is good.
- a paper coated with the whitening pigment of the present invention has a smaller weight than papers coated with the above described inorganic pigment, thus resulting in reduction of the transporting cost.
- X can be same or different hydrogen atom, methyl, ethyl, methoxy, ethoxy group, chlorine atom or sulfo group. Above all, the most suitable one is represented by the following General Formula (III):
- R 1 is an alkyl group such as methyl, ethyl, propyl, butyl, dodecyl or octadecyl group, an aralkyl group such as benzyl group, an aryl group such as phenyl group, an alicyclic group such as cyclohexyl group or a five-membered or six-membered heterocyclic group formed with N atom, such as pyrrolidine, piperidine, morpholine or pyridine group, R 2 , R 3 and R 4 are independently hydrogen atoms or groups represented by R 1 and Y is a quaternary ammonium salt of a halogen atom, preferably chlorine atom, examples of which are represented by the following formulas:
- the pigment component of the present invention can, for example, be prepared as follows.
- a sodium salt of a bis-styryl-biphenyl represented by the foregoing General Formula (III) is added to a suitable amount of water and is then subjected to heating and dissolving at about 60° C. with agitation, in which an equivalent or excessive amount of the above described quaternary ammonium compound, dissolved in a suitable amount of water, is poured.
- a white precipitate is deposited and the mixture is heated and stirred at the above described temperature for about 1 hour after the pouring to comlete the reaction.
- the deposited precipitate is filtered, adequately washed with water and dried at at most 100° C. to obtain a pure white powder of the object complex salt.
- the thus obtained white pigment component is provided as a white pigment composition in known forms, for example, in the form of a powder, aqueous dispersion, organic solvent dispersion or paste.
- the organic solvent used herein includes alcohols, esters, ethers, halogen compounds, hydrocarbons, ketones, etc, illustrative of which are butyl alcohol, ethyl acetate, Cellosolve, trichloroethylene, xylene, turpentine oil, solvent naphtha, methyl ethyl ketone, and the like.
- the grain diameter range of the pigment component of the present invention is preferably 1 to 2 ⁇ m for paper coating, plastic additives, textile printing, etc., 0.5 to 1.0 ⁇ m for photographic papers, ink jet inks, etc., 0.5 to 2.0 ⁇ m for baking finish and at most 5 ⁇ m for synthetic leathers.
- Preparation of the pigment compositions in these forms is generally carried out by dry or wet process using known pulverizers, for example, ball mills, sand mills, speed line mills and jet mills. If necessary, the pigment composition is converted into an aqueous dispersion with a surfactant and water using the above described pulverizers and then subjected to spray drying to prepare a powdered dispersion composition.
- pulverizers for example, ball mills, sand mills, speed line mills and jet mills.
- a suitable known surfactant is generally used.
- a suitable one is mainly selected from anionic and nonionic active agents, but in particular, nonionic active agents are preferably used.
- commonly used known additives for such pigment compositions for example, antigelling agents, protective colloids, antiseptics or wetting agents can be added thereto.
- a suitable pigment concentration is 5 to 50%, preferably 20 to 35% in water or organic solvents.
- the important feature of the white pigment composition according to the present invention consists in excellent hiding power as well as high whiteness.
- the whiteness and hiding power of the thus resulting black board paper and Kinshapaper were compared to obtain results as shown in Table 2.
- Table 2 the larger is the numerical value, the more excellent is the whiteness.
- the numerical value of Whiteness (W) shown in Table 2 was obtained from values of Y and Z, measured by means of a color difference meter of SZ- ⁇ 90 type (commercial name), manufactured by Nippon Denshoku KK, by which any five sites of an object were taken and subjected to measurement and an average value was obtained.
- the Kinshapaper and Blackboard Paper having the whitening pigment composition coated according to the present invention are all more excellent in whiteness than those using titanium oxide. This teaches that our whitening pigment composition is also excellent in hiding power.
- Another feature of the pigment composition of the present invention consists in that the density of the pigment component composing it is smaller than that of inorganic pigment components because of being organic. This means, for example, that when preparing an aqueous dispersion using the pigment composition of the present invention, grains of the pigment component are hard to be settled and the storage stability of the pigment component is improved.
- the present pigment composition-coated paper has a smaller weight than papers coated with inorganic pigment-compositions, resulting in reduction of transporting costs and mailing costs.
- Comparison of the densities of the pigment composition of the present invention for example, represented by the following structural formula:
- the pigment component of the present invention has a density of at most 1 ⁇ 2 times as large as clay having the smallest density of inorganic pigment components.
- the densities shown in Table 3 are measured by a method using a specific gravity bottle of the solid specific gravity measuremnt methods according to JIS Z 8807.
- the organic pigment component of the present invention is that it is excellent in miscibility with various binders such as gelatin, styrene-butadiene type, polyvinyl acetate type, acryl-styrene type (co-)-polymers, acrylic acid esters polymers, etc., gelling inhibitors, protective colloids and preservatives.
- the pigment components of the present invention are suitable as a base for coating agents of surface-coated papers, in particular, photographic printing papers or coated papers.
- Uvitex CBS-X (—commercial name—fluorescent whitening agent manufactured by Ciba Geigy Co., containing sodium salt of the foregoing formula (III) as an effective component) was added to 1000 ml of water, heated at about 60° C. and dissolved with agitation.
- 300 ml of Catiogen PAN (commercial name—cationic surfactant manufactured by Daiichi Kogyo Seiyaku KK) was poured therein, then reacted at the above described temperature for about 1 hour, and the precipitated crystals were filtered, washed with water and dried at 100° C., thus obtaining 192 g of pure white powder.
- This powder is a complex salt, one of the pigment components of the present invention, represented by the following formula.
- Pigment Component of Present 25.0% Invention Preparation Example 1 Emulsit 9 (-commercial name-) 1.0% Neugen EA-130T (-commercial 0.4% name-) Water 73.6% Total 100.0%
- the mixed liquid having the above described composition was pulverized and dispersed by means of a sandmill until the average grain diameter was at most 0.5 ⁇ m to thus obtain an aqueous dispersion composition of a fluorescent organic white pigment comprising 25.0% concentration of the pigment component and being excellent in hiding power.
- Emulsit 9 and Neugen EA-130T are all nonionic surfactants manufactured by Dauich Kogyo Seiyaku KK.
- a mixture comprising 25 kg of the white pigment powder obtained in Preparation Example 1 of Pigment Component, 8.4 kg of a butyral dispersed resin and 66.6 kg of ethanol was subjected to a pulvering treatment using Sand Grinder of continuous and vertical type (—commercial name—manufactured by Igarashi Kikai Seizo KK) until the average grain diameter was 0.3 to 0.4 ⁇ m to thus obtain a dispersion composition in an alcohol medium.
- a surface coating composition of paper having the following composition was prepared:
- the above described composition was coated onto a commercially available high quality paper to give a coating amount of 15 g/cm 2 using Wire Rod No. 14 (—commercial name—) at room temperature and dried at 120° C. for 1 minute.
- the resulting coated paper exhibited much clearer whiteness, luster and smoothness as compared with a paper coated with a coating composition using titanium oxide in place of the white pigment ultra-fine powder of the present invention in the above described coating composition.
- a polyethylene with a density of 0.925 g/cm 2 containing a fluorescent white pigment ultra-fine powder (Preparation Example 3) of the present invention in a proportion of 10% of the polyethylene was coated onto a photographic paper of a coating weight ratio of 150 g/m 2 containing a sizing agent and wet strengthening agent to give a thickness of 40 ⁇ m, which was further subjected to a high frequency corona discharge treatment.
- the back side was further coated in the similar manner to the right surface with a mixture of polyethylene having a density of 0.925 g/cm 2 and polyethylene having a density of 0.955 g/cm 2 in a mixing ratio of 1:1 to obatin a thickness of 45 ⁇ m.
- the thus obtained polyethylene-coated photographic paper containing the fluorescent whitening pigment of the present invention exhibited much clearer whiteness, which was then maintained even after coating of photographic emulsions and other photographic processings.
- a white paint composition for drying at normal temperature having the following mixing proportions was prepared:
- This composition is suitable as a coloring material for an ink jet, capable of giving a white image and excellent in brightening property, water-proof property and storage stability. Furthermore, this composition is free from clogging with the pigment at the end of the ink jet.
- NK-Couper A-1 (-commercial name- 70 g acrylic copolymer, manufactured by Shin-Nakamura Kagaku Kogyo KK) Total 100 g
- a printing paste having the above described composition was printed on a cotton cloth in knwon manner, previously dried at 100° C. for 1-2 minutes and then heat-treated at 146° C. for 3 minutes. On the cotton cloth was obtained a clear white printed pattern excellent in feeling and washing fastness.
- Liquid Composition for Surface Skin Layer CRISVON 7367 SL (-commercial name- 100 g urethane resin liquid, solid com- ponent 35%, manufactured by Dai- Nippon Ink Kagaku Kogyo KK) White Pigment Ultra-fine Powder 25 g of Preparation Example 1 Methyl Ethyl Ketone 30 g Dimethylformamide 10 g Total 165 g Liquid Composition for Adhesive Layer CRISVON 4010 HV (-commercial name- 100 g thermal setting urethane resin liquid) CRISVON NX (-commercial name- 8 g isocyanate crosslinker) CRISVON Accel HM (-commercial name- 3 g crosslinking promoter) Dimethylformamide 5 g Toluene 5 g Total 121 g Composition for Surface Finish Layer GIOSILAC CLEAR L-0465 (-commercial 100 g name-, manufactured by Dai-Nippon Ink Kagaku Kogyo KK) GIOSILAC MAT L-04
- the above described liquid composition for a surface skin layer was coated onto a mold releasing paper by a doctor knife with a coating amount of 130 g/m 2 and then dried with hot air at 90 to 110° C. for 2 minutes.
- the above described liquid composition for an adhesive layer was then coated on the surface skin layer with a coating amount of 150 g/m 2 and simultaneously combined with a base cloth (cotton raising cloth, thickness 1 mm) at a suitable gap of lamination rolls, followed by drying with hot air at 110 to 130° C. for 2 minutes.
- the resulting assembly was then subjected to ageing at 50 to 60° C. for three days under wound-up state.
- the mold releasing paper was released and surface finishing was carried out for several times by gravure rolls using the above described liquid composition for surface finishing, thus obtaining an urethane synthetic leather having a clear whiteness.
- a pigment composition for baking finish having the above described composition was prepared. Using xylene as a thinner, this composition was spray-coated (film thickness 30-35 ⁇ m on dry base) on a soft steel plate of 0.8 mm thick using an air spray, allowed to stand (setting) at room temperature for 15 minutes and heat treated at 130° C. for 20 minutes. The thus resulting coating had a clear whiteness and good lustre.
- the organic fluorescent whitening pigment of the present invention is excellent in hiding power and the whiteness thereof is more excellent than that of inorganic white pigments such as titanium oxide, etc.
- the present white pigment composition is free from the concentration quenching phenomenon taking place when using general fluorescent whitening agent, so it can be used with a larger concentration.
- the white pigment of the present invention has excellent miscibility with various polymers, binders, surfactants or other additives because of being organic and very good dispersion stability as well as good storage property such that pigment components do not cause aggregation, nor seeding or separating during storage because of having smaller density.
- the white pigment of the present invention can favorably be added to polymers because of being excellent in heat resistance as well as miscibility with various polymers.
- the organic fluorescent whitening pigment components of the present invention can widely be applied to coating agents for papers, whiteness improvers of photographic papers, printing papers, etc., aqueous or oily paints for various coating purposes, whitening agents of dyes for ink jets, printing inks, pigments for crayons, pigments for printing or various polymers.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
- Paper (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
TABLE 1 | |
Anion Component | |
|
|
—X | |
1 | —H |
2 | —H |
3 | —H |
4 | —CH3 |
5 | —C2H5 |
6 | —OCH3 |
7 | —Cl |
8 | —SO3Na |
Cation Component | |
|
|
—R1 | —R2 | —R3 | —R4 | Remarks | |||
1 | —C12H25 | —CH3 | —CH3 |
|
|||
2 | —C12H25 | —CH3 | —CH3 | —CH3 | |||
3 |
|
—C18H37 | Condensed Heterocylic Ring of R1, R2 and R3 | |
4 | —CH3 | —CH3 | —CH3 | —CH3 | |
5 | —C12H25 | —C18H37 | —CH3 | —CH3 | |
6 |
|
—CH3 | —CH3 | —C12H25 | |
7 |
|
—CH3 | —C12H25 | Condensed Heterocylic Ring of R1 and R2 | ||
8 |
|
—CH3 | —C12H25 | Condensed Heterocylic Ring of R1 and R2 | ||
Wire Rod | No. 14, 30 (Blackboard Paper) | ||
Coating Temperature | Room Temperature | ||
Drying Condition | 120° C., 1 minute | ||
TABLE 2 | ||||
Y | Z | Whiteness (W) | ||
1 | Kinshapaper of | 80.59 | 92.32 | 71.01 | ||
Original | ||||||
2 | Kinshapaper by | 88.13 | 117.07 | 132.24 | ||
Our Invention | ||||||
3 | Kinshapaper of | 84.95 | 97.54 | 75.61 | ||
Titanium Oxide | ||||||
4 | Black Board Paper | 4.68 | 5.55 | 4.76 | ||
of Original | ||||||
5 | Black Board Paper | 78.40 | 108.69 | 133.04 | ||
by Our Invention | ||||||
6 | Black Board Paper | 70.60 | 88.10 | 86.68 | ||
of Titanium Oxide | ||||||
Note: | ||||||
Whiteness (W) is Taube Whiteness, calculated by the following formula, in which the measured values of Y and Z are inserted. This is an index for showing the surface whiteness of papers or pulps, commonly used in the technical field of papers and pulps. | ||||||
Taube Whiteness = 4 × 0.847Z − 3Y |
TABLE 3 | |||
Pigment Component | Density | ||
Present Invention | 1.1 | ||
Clay | 2.46-2.63 | ||
Talc | 2.6-2.8 | ||
Titanium Oxide | 3.7-3.9 | ||
Calcium Carbonate | 2.83 | ||
Zinc Oxide | 5.4-5.7 | ||
Pigment Component of Present | 25.0% | ||
Invention (Preparation Example 1) | |||
Emulsit 9 (-commercial name-) | 1.0% | ||
Neugen EA-130T (-commercial | 0.4% | ||
name-) | |||
Water | 73.6% | ||
Total | 100.0% | ||
White Pigment Ultra-fine Powder | 25.0 g | ||
of Preparation Example 2 | |||
Sodium Hexametaphosphate | 0.3 g | ||
Alon T-40 (-commercial name- | 0.25 g | ||
anionic dispersant, manufactured | |||
by Toa Gosei Kagaku Kogyo KK) | |||
Latex (JSR 0692) | 6.3 g | ||
25% aqueous ammonia solution | 0.7 g | ||
Water | 67.45 g | ||
Total | 100.0 g | ||
Water | 52.5 g | ||
Tamor 731 (25%, -commercial name- | 9.0 g | ||
anionic surfactant, manufactured | |||
by R & H Co.) | |||
Neugen EA-120 (-commercial | 2.2 g | ||
name- nonionic surfactant manu- | |||
factured by Daiichi Kogyo Seiyaku KK) | |||
White Pigment Ultra-fine Powder | 275.0 g | ||
of Preparation Example 1 | |||
Ethylene Glycol | 50.0 g | ||
Defoaming Agent | 2.0 g | ||
25% aqueous ammonia solution | 1.0 g | ||
Boncoat EC-880 (50%, -commercial name- | 853.8 g | ||
acryl-styrene emulsion, manufactured | |||
by Dainippon Ink Kagaku Kogyo KK) | |||
High Molecular Emulsion Thickener | 34.8 g | ||
Texanol SC-12 (-commercial name- | 60.7 g | ||
silicone resin film making aid, | |||
manufactured by Chisso KK) | |||
Total | 1341.0 g | ||
White Pigment Ultra-fine Powder | 30 g | ||
of Preparation Example 2 | |||
NK-Couper A-1 (-commercial name- | 70 g | ||
acrylic copolymer, manufactured | |||
by Shin-Nakamura Kagaku Kogyo KK) | |||
Total | 100 g | ||
Polyvinyl Chloride | 650 g | ||
Dioctyl Phthalate | 350 g | ||
Stabilizer (based on polymer) | 2% | ||
White Pigment Ultra-fine Powder | 15% | ||
of Preparation Example 3 | |||
Liquid Composition for Surface Skin Layer |
CRISVON 7367 SL (-commercial name- | 100 g | |
urethane resin liquid, solid com- | ||
ponent 35%, manufactured by Dai- | ||
Nippon Ink Kagaku Kogyo KK) | ||
White Pigment Ultra-fine Powder | 25 g | |
of Preparation Example 1 | ||
Methyl Ethyl Ketone | 30 g | |
Dimethylformamide | 10 g | |
Total | 165 g |
Liquid Composition for Adhesive Layer |
CRISVON 4010 HV (-commercial name- | 100 g | |
thermal setting urethane resin liquid) | ||
CRISVON NX (-commercial name- | 8 g | |
isocyanate crosslinker) | ||
CRISVON Accel HM (-commercial name- | 3 g | |
crosslinking promoter) | ||
Dimethylformamide | 5 g | |
Toluene | 5 g | |
Total | 121 g |
Composition for Surface Finish Layer |
GIOSILAC CLEAR L-0465 (-commercial | 100 g | ||
name-, manufactured by Dai-Nippon | |||
Ink Kagaku Kogyo KK) | |||
GIOSILAC MAT L-0465 (-commercial | 50 g | ||
name-) | |||
Thinner | 50 g | ||
Total | 200 g | ||
White Pigment Ultra-fine Powder | 70 g | ||
of Compound No. 6 in Table 1 | |||
Commercially Available | 116.7 g | ||
Coconut Oil Alkyd Resin | |||
n-Butylated Melamine Resin | 50 g | ||
Total | 236.7 g | ||
Claims (11)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9297073A JPH11130975A (en) | 1997-10-29 | 1997-10-29 | Fluorescent organic white pigment composition excellent in opacifying properties |
US09/394,502 US6488867B1 (en) | 1997-10-29 | 1999-09-13 | Organic fluorescent whitening pigment composition having an excellent hiding power |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9297073A JPH11130975A (en) | 1997-10-29 | 1997-10-29 | Fluorescent organic white pigment composition excellent in opacifying properties |
US09/394,502 US6488867B1 (en) | 1997-10-29 | 1999-09-13 | Organic fluorescent whitening pigment composition having an excellent hiding power |
Publications (1)
Publication Number | Publication Date |
---|---|
US6488867B1 true US6488867B1 (en) | 2002-12-03 |
Family
ID=26560985
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/394,502 Expired - Fee Related US6488867B1 (en) | 1997-10-29 | 1999-09-13 | Organic fluorescent whitening pigment composition having an excellent hiding power |
Country Status (2)
Country | Link |
---|---|
US (1) | US6488867B1 (en) |
JP (1) | JPH11130975A (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006113183A1 (en) | 2005-04-18 | 2006-10-26 | Dow Corning Corporation | Architectural coating compositions containing silicone resins |
EP2042567A1 (en) * | 2007-09-18 | 2009-04-01 | Pitney Bowes Inc. | Postal-compliant fluorescent inkjet papers, inks for preparing them and individualized postage stamps printed thereon |
US20100083872A1 (en) * | 2007-04-27 | 2010-04-08 | Nippon Sheet Glass Company, Limited | Bright pigment, and bright coating composition and automotive body coating each containing the same |
US20100129412A1 (en) * | 2007-04-18 | 2010-05-27 | Nippon Sheet Glass Company, Limited | Bright pigment and cosmetic composition using the same |
US20100137488A1 (en) * | 2006-04-21 | 2010-06-03 | Nippon Glass Company, Limited | Bright Pigment, Method for Producing the Pigment, and Waterborne Resin Composition Containing the Pigment |
US20100227181A1 (en) * | 2007-10-18 | 2010-09-09 | Nippon Sheet Glass Company, Limited | Bright pigment |
US20100249304A1 (en) * | 2006-08-29 | 2010-09-30 | Nippon Sheet Glass Company, Limited | Pearlescent pigment |
EP2436739A1 (en) * | 2010-09-30 | 2012-04-04 | Brother Kogyo Kabushiki Kaisha | Treatment solution for ink-jet recording, water-based ink set for ink-jet recording, ink-jet recording method, and ink-jet recording apparatus. |
TWI494386B (en) * | 2010-02-26 | 2015-08-01 | Zebra Co Ltd | W / O type emulsion ink compositions and writing utensils for writing utensils |
DE102022205390A1 (en) | 2022-05-30 | 2023-11-30 | Henkel Ag & Co. Kgaa | Detergent-active compounds |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP6256029B2 (en) * | 2014-01-20 | 2018-01-10 | 株式会社リコー | Ink, ink cartridge using the same, and inkjet image forming apparatus |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3871898A (en) * | 1969-11-14 | 1975-03-18 | Ciba Geigy Ag | Process for the optical brightening of organic fibre material |
JPS57123262A (en) * | 1981-01-26 | 1982-07-31 | Showa Kagaku Kogyo Kk | Fluorescent brightener composition |
EP0060439A2 (en) * | 1981-03-14 | 1982-09-22 | Bayer Ag | Spinning mass containing an optical bleaching agent for the preparation of regenerated cellulose fibres |
US4888128A (en) * | 1986-12-18 | 1989-12-19 | Bayer Aktiengesellschaft | Paper-coating slips containing fluorescent brighteners |
US5177128A (en) * | 1985-07-10 | 1993-01-05 | Sequa Chemicals, Inc. | Paper coating composition |
JPH06122674A (en) | 1992-10-13 | 1994-05-06 | Hatsukoole Chem Kk | Organic white pigment |
US5622749A (en) * | 1993-05-08 | 1997-04-22 | Ciba-Geigy Corporation | Fluorescent whitening of paper |
EP0915370A1 (en) * | 1997-11-04 | 1999-05-12 | Konica Corporation | Silver halide light-sensitive photographic material |
JPH11129613A (en) * | 1997-11-04 | 1999-05-18 | Konica Corp |
-
1997
- 1997-10-29 JP JP9297073A patent/JPH11130975A/en active Pending
-
1999
- 1999-09-13 US US09/394,502 patent/US6488867B1/en not_active Expired - Fee Related
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3871898A (en) * | 1969-11-14 | 1975-03-18 | Ciba Geigy Ag | Process for the optical brightening of organic fibre material |
JPS57123262A (en) * | 1981-01-26 | 1982-07-31 | Showa Kagaku Kogyo Kk | Fluorescent brightener composition |
EP0060439A2 (en) * | 1981-03-14 | 1982-09-22 | Bayer Ag | Spinning mass containing an optical bleaching agent for the preparation of regenerated cellulose fibres |
US5177128A (en) * | 1985-07-10 | 1993-01-05 | Sequa Chemicals, Inc. | Paper coating composition |
US4888128A (en) * | 1986-12-18 | 1989-12-19 | Bayer Aktiengesellschaft | Paper-coating slips containing fluorescent brighteners |
JPH06122674A (en) | 1992-10-13 | 1994-05-06 | Hatsukoole Chem Kk | Organic white pigment |
US5514213A (en) | 1992-10-13 | 1996-05-07 | Hakkol Chemical Co., Ltd. | Organic white pigment |
US5606055A (en) | 1992-10-13 | 1997-02-25 | Hakkol Chemical Co., Ltd. | Organic white pigment |
US5622749A (en) * | 1993-05-08 | 1997-04-22 | Ciba-Geigy Corporation | Fluorescent whitening of paper |
EP0915370A1 (en) * | 1997-11-04 | 1999-05-12 | Konica Corporation | Silver halide light-sensitive photographic material |
JPH11129613A (en) * | 1997-11-04 | 1999-05-18 | Konica Corp |
Non-Patent Citations (1)
Title |
---|
Translation for JP 11-129613. * |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090030111A1 (en) * | 2005-04-18 | 2009-01-29 | Dow Corning Corporation | Architectural Coating Compositions Containing Silicone Resins |
WO2006113183A1 (en) | 2005-04-18 | 2006-10-26 | Dow Corning Corporation | Architectural coating compositions containing silicone resins |
US7807744B2 (en) | 2005-04-18 | 2010-10-05 | Dow Corning Corporation | Architectural coating compositions containing silicone resins |
US9045643B2 (en) | 2006-04-21 | 2015-06-02 | Nippon Sheet Glass Company Limited | Bright pigment, method for producing the pigment, and waterborne resin composition containing the pigment |
US20100137488A1 (en) * | 2006-04-21 | 2010-06-03 | Nippon Glass Company, Limited | Bright Pigment, Method for Producing the Pigment, and Waterborne Resin Composition Containing the Pigment |
US20100249304A1 (en) * | 2006-08-29 | 2010-09-30 | Nippon Sheet Glass Company, Limited | Pearlescent pigment |
US8273171B2 (en) | 2006-08-29 | 2012-09-25 | Nippon Sheet Glass Company, Limited | Pearlescent pigment |
US20100129412A1 (en) * | 2007-04-18 | 2010-05-27 | Nippon Sheet Glass Company, Limited | Bright pigment and cosmetic composition using the same |
US9107834B2 (en) | 2007-04-18 | 2015-08-18 | Nippon Sheet Glass Company, Limited | Bright pigment and cosmetic composition using the same |
US20100083872A1 (en) * | 2007-04-27 | 2010-04-08 | Nippon Sheet Glass Company, Limited | Bright pigment, and bright coating composition and automotive body coating each containing the same |
US8440014B2 (en) | 2007-04-27 | 2013-05-14 | Nippon Sheet Glass Company, Limited | Bright pigment, and bright coating composition and automotive body coating each containing the same |
US7973098B2 (en) | 2007-09-18 | 2011-07-05 | Pitney Bowes Inc. | Postal-compliant fluorescent inkjet papers, inks for preparing them and individualized postage stamps printed thereon |
EP2042567A1 (en) * | 2007-09-18 | 2009-04-01 | Pitney Bowes Inc. | Postal-compliant fluorescent inkjet papers, inks for preparing them and individualized postage stamps printed thereon |
US20100227181A1 (en) * | 2007-10-18 | 2010-09-09 | Nippon Sheet Glass Company, Limited | Bright pigment |
US8409708B2 (en) * | 2007-10-18 | 2013-04-02 | Nippon Sheet Glass Company, Limited | Bright pigment |
TWI494386B (en) * | 2010-02-26 | 2015-08-01 | Zebra Co Ltd | W / O type emulsion ink compositions and writing utensils for writing utensils |
EP2436739A1 (en) * | 2010-09-30 | 2012-04-04 | Brother Kogyo Kabushiki Kaisha | Treatment solution for ink-jet recording, water-based ink set for ink-jet recording, ink-jet recording method, and ink-jet recording apparatus. |
US8690304B2 (en) | 2010-09-30 | 2014-04-08 | Brother Kogyo Kabushiki Kaisha | Treatment solution for ink-jet recording, water-based ink set for ink-jet recording, ink-jet recording method, and ink-jet recording apparatus |
DE102022205390A1 (en) | 2022-05-30 | 2023-11-30 | Henkel Ag & Co. Kgaa | Detergent-active compounds |
Also Published As
Publication number | Publication date |
---|---|
JPH11130975A (en) | 1999-05-18 |
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